The invention relates to electroluminescent assemblies containing conductive polymers as auxiliary layers.
An electroluminescent (xe2x80x9cELxe2x80x9d) assembly is characterized by the emission of light and the flow of electric current when an electric potential is applied. Such assemblies have long been known in industry under the name light emitting diodes (xe2x80x9cLEDsxe2x80x9d). The emission of light occurs as a result of positive charges (holes) and negative charges (electrons) combining with emission of light.
The LEDs customary in industry mostly comprise inorganic semiconductor materials. However, EL assemblies for which the essential constituents are organic materials have been known for some years. These organic EL assemblies generally contain one or more layers of organic charge transport compounds.
The general layer structure is as follows, where the numbers 1 to 10 have the following meanings:
1. Support, substrate
2. Base electrode
3. Hole injection layer
4. Hole transport layer
5. Emitter layer
6. Electron transport layer
7. Electron injection layer
8. Top electrode
9. Contacts
10. Envelope, encapsulation
This structure represents the most general case and can be simplified by leaving out individual layers, in which case at least one of the remaining layers assumes a plurality of functions. In the simplest case, an EL assembly comprises two electrodes between which an organic layer fulfills all functions, including the emission of light. Such systems are described, for example, in the PCT patent application WO-A 90/13148 on the basis of poly[p-phenylene-vinylene].
In the production of large-area, electroluminescent display elements, at least one of the electrodes 2 or 8 that supply electric power must consist of a transparent and conductive material.
Suitable substrates 1 are transparent supports such as glass or films of plastic such as polyester, for example, polyethylene terephthalate or polyethylene naphthalate, polycarbonate, polyacrylate, polysulfone, or polyimide.
Suitable transparent and conductive materials are
(a) metal oxides, for example, indium-tin oxide (xe2x80x9cITOxe2x80x9d) and tin oxide (xe2x80x9cNESAxe2x80x9d);
(b) semitransparent metal films of, for example Au, Pt, Ag, Cu, and the like.
Suitable emitter layers 5 are described in DE-A 19,627,071. However, in practice it has been found that electron injection or hole injection layers (3,4 and/or 6,7) must be incorporated into the electroluminescent assemblies to increase the light flux. EP-A 686,662 discloses the use of specific mixtures of conductive organic polymers, such as 3,4-polyethylenedioxythiophene and polyhydroxy compounds or lactams, as electrode 1 in ELP assemblies. However, in practice it has been found that these electrodes have insufficient conductivity, particularly for large-area displays.
DE-A 19,627,071 discloses the use of polymeric organic conductors, for example, 3,4-polyethylenedioxythiophene, as hole injection layers. By this means, the light flux of the electroluminescent displays can be increased considerably compared with assemblies not having intermediate, organic polymer layers. However, the life of these displays is still not sufficient for practical applications.
It was an object of the present invention to increase the life of ELP assemblies based on organic materials.
It has now surprisingly been found that the life of electroluminescent displays to be increased considerably by using a solution or dispersion of polymeric organic conductors having a very small particle size and, if conductive polymers of the formula (I) are used, a specific ratio of the conductive polycations to nonconductive counterions or nonionic binders. It has also been found that the occurrence of short circuits between the two conductive electrodes 2 and 8 can be significantly reduced in this way.
The present invention relates to an electroluminescent assembly containing, as hole injection layer, a polymeric organic conductor that has been applied either from solution or from a dispersion and contains particles, even in any swollen state, having a particle size of less than 1 xcexcm (preferably less than 0.5 xcexcm, particularly less than 0.25 xcexcm).
Suitable polymeric organic conductors are substituted or unsubstituted polyfurans, polypyrroles, polyanilines or polythiophenes. Such compounds are described, for example, in EPA 2,257,573 (polyalkoxythiophenes), WO-A 90/04256 (polyanilines), EP-A 589,529 (polypyrrole), and DE-A 2,262,743 (oligoanilines). Particularly suitable polymeric organic conductors are uncharged or cationic, soluble or insoluble alkylene-dioxythiophenes of the formula (I) 
wherein
n represents an integer from 5 to 100 and
R represents H, a substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, xe2x80x94CH2xe2x80x94OH, or an aryl radical having 6 to 14 carbon atoms.
Examples of particularly suitable alkylenedioxythiophenes are described in EP-A 440,957 and DE-A 4,211,459.
Polymeric organic conductors that are likewise particularly suitable are uncharged or cationic, soluble or insoluble polythiophenes of the general formula (II) 
wherein
n represents an integer from 5 to 100,
R1 represents xe2x80x94(CH2)mxe2x80x94SO3M, where M is Li, Na, K, Rb, Cs, NH4, or H,
R2 represents H or an alkyl group having from 1 to 12 carbon atoms, and
m represents an integer from 1 to 12.
The preparation of these polythiophenes is described in WO-A 98/03499.
Polythiophenes of the formulas (I) and (II) can be used alone or as a mixture.
Particular preference is given to conductive polymers of the formula (I) in combination with polyanions, such as are described, for example, in EP-A 440,957. Particularly suitable solutions or dispersions of conductive polymers are obtained when less than 0.4 part by weight (particularly less than 0.3 part by weight), based on one part by weight of polyanion, of the conductive polymer of the formula (I) is present.
This ratio of conductive polymer to polyanion can be set directly in the preparation. However, it has been found that it is also possible to start from a solution or dispersion containing a higher proportion of conductive polymer and to set the ratio of conductive polymer to polyanion according to the invention only subsequently by addition of salts of the polyanions or free acids of the polyanions.
In addition, these preferred solutions or dispersions have the advantage that the conductivity of the layer is less than that obtained using a solution or dispersion having a ratio of the polythiophene of the formula (I) to polyanion of 0.4:1. This reduces the xe2x80x9ccross talkxe2x80x9d (see Braun in Synth. Metals, 92, 107-113 (1998)) in electroluminescent matrix displays. For this reason, preference is given to using solutions or dispersions that lead to layers having a surface resistance of  greater than 105 xcexa9/xe2x96xa1 measured at a dry film thickness of 75 nm or layers having a conductivity of  less than 2 S/cm.
The electroluminescent assembly of the invention is produced by means of technologies that are basically known. To produce the intermediate layers 3 in the systems of the invention, a solution or dispersion of the polythiophene is distributed as a film on the base electrode. Solvents used are preferably water or water/alcohol mixtures. Suitable alcohols are, for example, methanol, ethanol, propanol, isopropanol, and butanol. The use of these solvents has the advantage that further layers can be applied from organic solvents such as aromatic or aliphatic hydrocarbon mixtures without layer 3 being attacked.
The solutions or dispersions of the polymeric organic conductor are preferably filtered through a filter, for example, a membrane filter from Millipore, having a pore size of  less than 1 xcexcm prior to the coating step. Preference is given to using  less than 0.5 xcexcm filters, and particular preference is given to using  less than 0.25 xcexcm filters.
It is also possible to add organic polymeric binders and/or organic low molecular weight crosslinkers to the solutions or dispersions of the polymeric organic conductors. Appropriate binders are described, for example, in EP-A 564,911.
Preference is given to using solutions or dispersions of the polymeric organic conductors which contain less than 10 ppm of metal ions and/or less than 10 ppm of anions of inorganic acids. Particular preference is given to using solutions or dispersions of the polymeric organic conductors that contain less than 1 ppm of metal ions and/or less than 1 ppm of anions of inorganic acids.
The solution or dispersion of the polymeric organic conductor is uniformly distributed on the substrate using techniques such as spin coating, casting, doctor blade coating, printing, or curtain casting. The layers are subsequently dried at room temperature or at temperatures up to 300xc2x0 C. (preferably up to 200xc2x0 C.).
The solution or dispersion can also be applied in structured form, preferably by printing techniques such as ink jet printing. This technique is described for water-soluble polythiophenes in, for example, Science, Vol. 279 (1998).
It has been found that when use is made of supports for which the full area has been coated with indium-tin oxide and to which the conductive polymer layer has been applied in structured form, the emitter layer that is subsequently likewise applied over the full area emits light only at the places that are coated with conductive polymer. This method makes it possible to produce structured electroluminescent displays in a simple way without structuring of the conductive base electrode.
The thickness of the intermediate layer 3 according to the invention is from about 3 to 500 nm (preferably from 10 to 200 nm).
Subsequently, the further layers are applied by deposition from solution or by vapor deposition to the intermediate layer 3 produced according to the invention. Preference is given to using poly-para-phenylene-vinylene derivatives or aluminum complexes such as aluminum quinolate as emitter layer 5. When using poly-para-phenylene-vinylene derivatives, the additional hole injection layer 4 can advantageously be omitted.
The electroluminescent displays produced according to the invention are notable for a long life, a high light flux, and low voltages in use.